US3690771A - Method and apparatus for instrumentally shading metallic paints - Google Patents

Method and apparatus for instrumentally shading metallic paints Download PDF

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US3690771A
US3690771A US3690771DA US3690771A US 3690771 A US3690771 A US 3690771A US 3690771D A US3690771D A US 3690771DA US 3690771 A US3690771 A US 3690771A
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color
standard
paint
delta
batch
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William S Armstrong Jr
Webster H Edwards
Joseph P Laird
Roy H Vining
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E I du Pont de Nemours and Co
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E I du Pont de Nemours and Co
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRA-RED, VISIBLE OR ULTRA-VIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/46Measurement of colour; Colour measuring devices, e.g. colorimeters
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRA-RED, VISIBLE OR ULTRA-VIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/46Measurement of colour; Colour measuring devices, e.g. colorimeters
    • G01J3/463Colour matching
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRA-RED, VISIBLE OR ULTRA-VIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/46Measurement of colour; Colour measuring devices, e.g. colorimeters
    • G01J3/465Measurement of colour; Colour measuring devices, e.g. colorimeters taking into account the colour perception of the eye; using tristimulus detection
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRA-RED, VISIBLE OR ULTRA-VIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/46Measurement of colour; Colour measuring devices, e.g. colorimeters
    • G01J3/50Measurement of colour; Colour measuring devices, e.g. colorimeters using electric radiation detectors
    • G01J3/504Goniometric colour measurements, for example measurements of metallic or flake based paints
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRA-RED, VISIBLE OR ULTRA-VIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/46Measurement of colour; Colour measuring devices, e.g. colorimeters
    • G01J2003/466Coded colour; Recognition of predetermined colour; Determining proximity to predetermined colour

Abstract

A system which can be used in the paint manufacturing industry to shade batches of paint to desired standard color based on standard values for the standard color by use of physical differences of the paint to be shaded and the standard paint determined from tristimulus values derived from panels sprayed with the respective paints.

Description

United States Patent Armstrong Jr. et al.

[:41 METHOD AND APPARATUS FOR INSTRUMENTALLY SHADING METALLIC P INTs [73] Assignee: E. l. du Pont de Nemours and Company, Wilmington,-Del.

22 Filed: April 7, 1970 21 A 1.N6.=26,269

52 US. Cl. ..356/176,250/226, 356/74,

- 356/96 51] int. Cl. ..G01j 3/46, G01 j 3/42 [58] Field of Search ...356/96, 176, 178, 74; 250/226 51 Sept. 12,1972

OTHER PUBLICATIONS Color Technology" by Marshall; Chemical Engineering, Aug. 12, 1968; pg. 148- 156 r Digital Computer Color Matching; Allen; American Dyestufi Reporter, pg. 57- 63.

Paint Testing Manual; Gardner & Sward; Gardner Laboratory, Inc.; Bethesda, Maryland, March 62; pg., 21, 22,12,13.

Primary Examiner-Ronald L. Wibert Assistant Examiner-V. P. McGraw Attorney-John E. Griffiths [57] ABSTRACT A system which can be used in the paint manufacturing industry to shade batches of paint to desired standard color based on standard values for the standard color by use of physical differences of the paint to be shaded and the standard paint determined from [56] References tristimulus values derived from panels sprayed with v UNITED STATES PATENTS the respectlve palms- 3,506,365 4/1970 Hunt et al ..356/96- 6 Claims, 1 Drawing Figure l A Al A1! PREPARATION OF MULTI- PIGMENTED PAINT WHICH IS TO REPRESENT THE STANDARD COLOR FOR THAT PARTICULAR SHADE PREPARATION OF SINGLE PIGMENT PAINTS FOR EACH PIGMENT USED IN THE PAINT OF A PREPARATION OF PAINT TO BE SHADED TO THE COLOR STANDARDS OF PAINT IN A REPRODUCIBLE MODE OF APPLICATION OF PAINTS TO TEST PANELS CALCULATION OF VECTOR DATA CHARACTERIZATION OF STANDARD COLORANTS BY SPECTRAL CURVES AND DETERMINATION or DIFFERENCES BETWEEN BATCH (A") AND STANDARD (A) a! I'RISTIMULUS READINGS or BATCH CONVERSION OF DATA BY PROGRAMMED COMPUTER DERIVED FROM C AND C'.

INTO AMOUNTS OF PIGMENT TO ADD FOR COLOR MATCH Patented Sept. 12, 1972 3,690,771

A A A PREPARATION OF MULTI- PREPARATION OF SINGLE PREPARATION OF PAINT PIGMENTED PAINT WHICH PIGMENT PAINTS FOR TO BE SHADED TO THE IS TO REPRESENT THE EACH PIGMENT USED IN COLOR STANDARDS OF STANDARD COLOR FOR THE PAINT OF A PAINT IN A THAT PARTICULAR SHADE REPRODUCIBLE MODE OF APPLICATION OF PAINTS TO TES PANELS CHARACTERIZATION OF ETERI-IIILZTIOII C STANDARD COLORANTS BY DIFFERENCES BETWEEN SPECTRAL CURVES AND BATCH (A") AND CALCULATION OF STANDARD (A) BY VECTOR DATA TRISTIMULUS READINGS OF BATCH CONVERSION OF DATA BY PROGRAMMER COMPUTER DERIVED FROM C AND C INTO AMOUNTS OF PIGMENT TO ADD FOR COLOR MATCH INVENTORS WILLIAM S. ARMSTRONG, JR. WEBSTER H. EDWARDS JOSEPH P. LAIRD ROY H. VINING W s. ATR mwm' METHOD AND APPARATUS FOR INSTRUMENTALLY SHADING METALLIC PAINTS BACKGROUND OF THE INVENTION In the manufacture of pigmented finishes one rarely if ever achieves a satisfactory color match versus a color standard without an adjustment process known as shading. Shading usually involves a relatively minor but critical manipulation of the formula pigment composi- 'tion, correcting for the cumulative effects of manufac turing variables on pigment dispersions.

Traditionally, the-shading process has been carried out by highly skilled and trained personnel who require extensive on-the-job experience to achieve proficiency in their craft. Since visual shading at best is an art, effective administration of the process'was difficult and, in many cases, the actual capacity of a plant was tied to the proficiency of the shaders. Displacement of the visual process has been slow and the lack of progress can be attributed to many factors. Visual color matching techniques have enjoyed a comparatively high measure of efficiency,a result of constantly refining procedures developed through the centuries. In addition, the normal eye is extremely sensitive to subtle color differences and it is only in the past to years that practical optical instrumentation has been developed that can rival or exceed the eye in measuring small-color differences. While investigators postulated mathematical expressions which attempted to characterize the optical characteristics of pigmented films, practical application was restricted due to the complexity of the mathematics involved and the sensitivity of instruments required. The computer age haschanged this.

The evolution and availability of high-speed, low cost digital computers has generated a new interest in a series of equations put forth by Kubelka and Munk in 1931. This hypothesis relates the effect of a scatter component (S) andan absorption component (K) in terms of measured reflectance. The popularity of the Kubelka-Munk equations among practical colorists ,coefficients. These characteristics were readily visualized and understood by the majority of colorists; whereas, prior mathematical treatments of color, though mathematically correct, were not understood nor completely trusted. Despite this advantage, the complexity and volume of calculations associated with the application of the hypothesis precluded usage until the advent of modern computational equipment. The application of Kubelka-Munk technology will be discussed in more details later.

Preliminary attempts were made to both formulate and to shade colors using spectrophoto'metric and tristimulus difference measurements but were successful in resolving only some of the commercial color problems. Progress was made in the area of shading nonmetallic colors as the reflectance of the paint was constant at varying viewing angles. a

The advent of the high glamor metallic finishes desired by the automotive industry created a perplexing problem. This type of finish exhibited a two-tone or flop effect, i.e., the color appeared different at different viewing angles. The techniques in use up to that time were unable to cope with this variable which was due to the reflectance of the metal particles dispersed in the paint film.

DESCRIPTION OF THE DRAWING In its broadest scope the automated shading system can be illustrated by the use of the drawing. Block A represents the manufacture of a batch of paint which is selected upon as being the standard to which subsequent batches will be shaded. Block A represents the preparation of paints containing only one pigment. This procedure is followed for each pigment which is a component of the paint of block A. At B the paints from A and A are applied to test panels by any method which will be uniform and reproducible in terms of the visual appearance of the paint for subsequent applications.

A Block C represents a means of obtaining colorant constants, in terms of Kubelka-Munk coefficient. Colorants are defined as a dispersion of pigment color, however, the system could function by determinations on pigments independent of any dispersion medium. The constants obtained through spectrophotometric measurements on the panels of B coated with the single pigment paints prepared in block A' are the absorption (K) and scattering (S) coefficients. These data are utilized to calculate the color adjustment or vector data (partial derivatives) for formulas (recipes) and are basic to the actual calculation of a shading adjustmentstep D. v

The aforementioned partial derivatives which are color constants for a given formula composition are punched into computer input cards using a binary cod ing system. The entire computer interaction. is represented by block D. The computer input cards can then be fed into a computer specially programmed to handle linear programming. .This computer is programmed so as to return a minimal positive solution in A" represents preparation of a batch of paint for which color standardization is sought relative to a known standard color which was prepared in A.

A sample of the paint prepared in A" is coated on a test panel using the same technique as B.

Block C represents determination of tristimulus values which in our coordinate system are designated G.R. B. values for the light reflectance exhibited by the batch test panel. These values can be obtained by use of a spectrophotometer or colorimeter modified for metallic measurements. Six values are used to compute the differences between the test panel and the standard utilizing a coordinate system such as C.I.E. C.I.E. Commission Internationale del lEclaige further described in Color Science, pages 238-321 by Gunter Wyszecki and W. S. Stiles published by .l. Wiley DESCRIPTION OF THE INVENTION Normally any paint program is initiated to satisfy the aesthetic desires of the customer. Once this desire for a particular color has been satisfied, a standard color to which all subsequent batches must comply in visual appearance is obtained. This is represented by A as previously indicated.

The transition from visual to instrumental procedures for color adjustment and control first necessitated the development of techniques that make possible the preparation of samples which are both repeatable by the same person in a given production area and reproducible by different people in different production areas and at different times. The advent of metallic colors created a perplexing situation in the area of repeatability and reproducibility.

An instrumental shading system requires the use of a system which could coat a test panel to a high degree of visual consistency. For the purpose of this invention a controlled environment spray system could be used to duplicate test panels even though these panels may be sprayed at different times by different individuals. Therefore, any coating system which produced panels coated so as to visually appear very similar would be satisfactory. This is especially important since paints containing metal flake particles must be applied so as to effectuate a reproducible degree of particle orientation in order that the paint film be visually similar. This system is represented by block B.

This preferred spray system which is symbolized by block B of the drawing satisfies the major criteria of reproducibility and repeatability. This system enables one to prepare test panels sprayed with the paint which has been deemed acceptable by the customer in order to accurately determine a set of standards to which future batches of paint can be directed. The same technique is later used to prepare panels with the paint which is to be standardized thereby precluding the application technique from influencing predicted corrections.

Obviously, any mode of paint application to a test panel that can be controlled in varying situations such as time, place, operator, etc., would be suitable for adoption into this system. A controlled environment spray system is merely illustrative of a preferred system.

The ability to reproducibly spray metallic colors by itself, does not make it possible to instrumentally color adjust and control production batches, Color theory and instrumentation applicable to colored films that change color with viewing or illuminating angle had to be evolved and then reduced to every-day practice.

Prior work with non-metallic colors indicated that the Modified Adams Coordinate System would be a preferable coordinate system selection because of its very excellent agreement with perceived color and its relative simplicity. The color values expressed in the Modified Adams Coordinate System define color in terms of lightness, hue and saturation, the three dimensions of color.

The lightness coordinate is based on a scale of zero to 100, where zero represents the perfect black and 100 the perfect white. Between the poles exist shades of neutral gray. The lightness of any color can be positioned on this scale. The hue and saturation characteristics of any color are represented by the a axis, the red/green attributes, the b axis, the yellow/blue attributes. The saturation of a color is defined as the distance of the a and b values from the neutral gray of the L axis. The greater the distance, the more saturated or cleaner the color.

Calculation of the L, a, b values from measured tristimulus values (block C) utilizes the cube root equation. L. G. Glasser, A. H. McKinney, C. D. Reilly, and P. D. Schnelle. Cube Root Color Coordinate System," Journal of the Optical Society of America, Vol. 48, pages 736-740, October, 1958.

The basic equations are:

a: 10 (RI/8 61/3) b= 42.34 (6" 8") where The Modified Adams System offers a degree of simplicity that is lacking in most other color order systems. Color differences existing between a batch and standard can be expressed as follows:

AL= L (batch) L (standard) Aa a (batch) a (standard) Ab b (batch) b (standard) AE= w/ (AL) (Aa) (Ab) The resultant values agree with visual assessment.

Positive values of AL indicate the batch is lighter than standard, negative values indicate the batch is darker than standard. Positive Aa values indicate the batch is redder (less green) than standard, negative Aa indicates the batch is greener (less red) than standard. Similarly positive Ab values indicate the batch is yellower (less blue) than standard, negative Ab indicates the batch is bluer (less yellow) than standard. AE is the total color difference.

Color adjustment data (vector) previously were obtained by manual means, that is, physically weighing predetermined amounts of colorants into known compositions (formulas). Vector data are no longer prepared manually but are calculated via digital equipment using formula pigmentcomposition and colorant characterization data. Colorant characterization data are derived from a series of color panels representing blends of each individual colorant with white and/or aluminum as characterized by block A. Spectrophotometric curves are run on these panels and the constants, K (absorption) and S (scatter) values are calculated (block C) from the basic Kubelka-Munk equation.

Where R is the measured reflectance of the color at a given wavelength.

Characterization procedures for colorants can be found described in the literature common to the color art. These procedures are absolute methods and are predicated on measurements made on panels exhibiting various levels of hiding. Accuracy was primarily dependent on ones ability to measure film thickness. Experience indicates that a large number of color and film thickness measurements were required to achieve even a moderate level of precision. Although these methods could be successfully utilized, a simpler method is preferred.

The need for multiple measurements was eliminated by a new characterization technique. This technique used a combination of the basic Kubelka-Munk equation, the Duncan equation D. R. Duncan, Journal of the Oil and Color Chemists Association, Vol. 32, page 296 (1949).) (discussed later) and panels prepared at complete hiding to provide colorant characterization data. The scattering and absorption coefficients resulting from the application of this technique are relative rather than absolute, being relative to the standard white (or aluminum) utilized. Simplicity was achieved by assuming a fixed value of the scattering coefficient (5,) for the standard white aluminum, or a mixture of white and aluminum used in characterization. Using this assumption, it is possible to calculate the absorption coefficient (K, for the reference colorant directly from the Kubelka-Munk equation. If

The K/S ratio of a mixture of a referencecolorant and a second colorant can be calculated using the Duncan equation.

(K/S),,, (C K,+ C K )/(C, S,+ C 5,)

tolerance. This is important since in a system containing more than four colorants, there are several possible mined are relative to a reference pigment or colorant,

depending on the projected use. The only restrictions placed on the calculated coefficients, K S are that data for colorants used ina given composition be relative to a common reference and secondly, that they be used in colors matched at essentially complete hiding.

The calculation of vector data for a given composition is straightforward. The concentrations of the colorants-are obtained from the formula, the K and S coefficients for each colorant have previously been determined with the result that the vector movement can be calculated differentially using the basic Duncan and Kubelka-Munk equations. The calculation of tristimulus valuesfrom reflectance data follows. This operation is characterized in block C of the drawing.

This data is then coded and punched onto a single input card for future use in the shading computer.

The manual aspects of both vector preparation and graphical shading economically restricted this early shading system to a few highly repetitive colors. These restrictions were overcome by the application of computers to the development of vectors (block C) and shading of batches (D of the drawing). Special-purpose analog shading computers now utilized and preferred were developed to solve the equations previously handled graphically. The computer is programmed for a positive solution in that all corrections to a batch are additions and are not takeouts, a characteristic of many digital programs. With takeouts, additional calculations are required to re-balance the formula. The computers of this invention are programmed in such a manner that the solution is the minimum addition of colorants required to adjust the batch to equal the standard color or to within a predetermined color solutions to a given color difference which can vary significantly in size.

In adapting color technology to metallic colors it was recognized that one would no longer be dealing with pigmented films that reflect light in an essentially diffuse pattern but would be faced with problems of directionality. Ideally, individual flake particles act like mirrors with their reflection efficiency being a function of their refractive index relative to the surrounding medium. Commercially available aluminum flake, however, is not optically flat but has an appearance in miniature of a crumpled piece of paper which has been partially smoothed out. The orientation of the flat and thin particles is rarely precisely parallel to the film surface and is more often semi-horizontal. Commercially available aluminums contain a fair portion of fine flake which because of their reduced size to thickness ratio are less likely to orientate themselves parallel to the film surface. These factors contribute to some dispersion of the directional characteristics of the reflected light.

, Superimposed upon the imperfections of aluminum flake are the effect of the other pigments employed in the finish. In most cases these are fine particle size pigments but because of dispersion limitations they do possess a degree of scatter, further reducing directionality.

The directional reflectance characteristic of a metallic film results in phenomena most commonly referred to as two-tone. Other names given this phenomena are flop,"flip-flop, flash, side-tone, etc. Twotone occurs when a panel is viewed at varying angles to incident light and by definition was considered to be the change in reflectance, AG. The two-tone value is expressed as the ratio of two reflectance values, equating the phenomena as a function of lightness.

Metallic colors were considered to possess four dimensions, and an acceptable match would occur when lightness, hue, saturation and two-tone were adjusted to nearly equal or equal that of the standard. Mathematically, the three equations utilized in adjusting solid colors were supplemented by the two-tone equation:

-AL N AL N gAL N,,AL, N,,AL,

Aa N Aa, N Aa N Aa N Aa -Ab N Ab, N Ab N Ab N ab,

ATT= NHAII, N,,A TT N,,ATT,+ N,,A Tr,

where:

-AL is lightness difference existing between batch and standard -Aa) is hue and saturation difference existing between Ab) batch and standard -ATT is two tone difference existing between batch and standard Aa,) is color movement (vector) f0; colorant l ATT, is two tone movement vector for colorant l N, is percent of vector concentration required for colorant 1 increased, resulting in the high glamor metallics of today.

As metallic colors increased in glamor, more and more metallic colors shaded in accordance with the four-dimensional concept were found to be visually objectionable though .instrumentally acceptable. These batches when viewed visually in a manner to exclude side-tone considerations were judged to be good matches versus standard. It was noted that both viewing and measuring geometry were very similar. When batch panels were viewed at an oblique angle, significant differences were noted. Viewing and measuring geometry was not similar. A colorimeter was modified so that it was possible to measure tristimulus values of the metallic panel from horizontal to near vertical positions. Measurements involving panels that were instrumentally acceptable under the four-dimensional concept but visually objectionable were found to exhibit color differences at all measuring angles in the 45, position where they were judged visually to be acceptable. Batches judged to be visually and instrumentally acceptable when measured in a similar manner were found to exhibit near zero color differences regardless of the angle measured.

The dependence of side-tone color on hue and saturation characteristics, indicated that lightness per se could not adequately characterize side-tone. Measurement studies had shown that visual color differences existing between two metallic colors were detectable at an infinite number of angles. Through analysis of data, measuring positions were selected that made it possible to accurately describe color differences existing between two metallic colors regardless of angle. Preferably, the angles should be from 60 to 80 apart from optimal readings. Equally important, it was demonstrated that when the measured differences were reduced to near zero, the colors matched each other regardless of viewing angle. Color-adjusting a metallic was therefore analogous to shading two colors simultaneously, adjusting each for lightness, hue and saturation. A metallic color can be described by six coordinate values and by six color differences. By this analogy metallic colors are said to have six dimensions, solid colors three dimensions.

A generalized form of the equations for metallics would, therefore, be

AL NC AL NC ALpg NCpaALpg Aap= NcnAa NC AC Ncp Aapa NC A nv AL NC ALH NC AL NCH3AL NC AL where F and H represent two different angles.

Color measurements are normally made using either a tristimulus colorimeter or a spectrophotometer.

The colorimeter was modified as previously mentioned to measure metallic colors at varying angles, preferably two distinct angles, making possible the calculation of the six dimensions that describe differences existing between two metallic colors. Although, measurements can be taken at a number of angles, only two are necessary for accurate determination of color properties. As previously indicated the gradient between these angles is preferably 60 to though any angular difference could produce meaningful results. It should be noted that the angles used should be similar, preferably plus or minus 10, more preferably plus or minus 5, for readings taken to obtainspectral curves and those taken to yield tristimulus values.

To calculate Kubelka-Munk constants, K (absorption) and S (scatter) values, for use with metallic colors, it was necessary to modify a spectrophotometer in a manner that made it possible to measure reflectance curves across the visible spectrum at multiangular positions (both in' a horizontal and vertical plane). The spectrophotometer modified for our use was the commercially available Bausch and Lomb 5 05, however any Spectrophotometer could be so modified after analysis of viewing geometry. The aforementioned spectrophotometric determinations are represented by block C of the drawing.

The data obtained is related to the shading and color prediction operation making feasible the calculation of colorant data for use with metallics. A library of data for a given colorant therefore consists of one set of data (K, S values at several wavelengths) for use in nonmetallic finishes and at least two sets of data for use with metallic finishes. These data are used to calculate vectors (block C) for at least two distinct angles for standard formulas as characterized by block A.

Tristimulus determinations are used to determine the A values described earlier for test panels coated with the paint which is to be color shaded to the color standard (set The tristimulus values are then transposed into the modified Adams Coordinates using the aforementioned cube root equations. The resultant L, a and b values serve to locate the color in color space. In comparing a batch versus a standard, color differences or delta values are obtained. These can be transposed into the single value E which can be used in the equation mentioned earlier with the Adams System. The National Bureau of Standards in Washington has defined an E value of 0.3 N.B.S. units as being only barely detectable to highly trained color personnel. A value of 1.0 N.B.S. unit is generally considered to be a good commercial match. Therefore, in view of the aforementioned procedures, to calculate a shading adjustment for a batch, the color differences existing between the batch and standard at multi-angles are determined using a colorimeter or spectrophotometer. These values plus the batch weight are then relayed to the'computer. The computer operator enters these data plus the computer input card containing the vector data into the computer.- The identity and amount. of the colorants required in the color addition that must be added to the batch in order to obtain a theoretically perfect match is then calculated. The addition is expressed in amounts of colorant to be added to the batch. Ideally, for nonmetallic colors, up to three colorants may be required, for metallic colors up to four colorants may be necessary. Utilizing color tolerance data, the computer operator can, if requested, determine the color addition required to adjust the batch to a'point just within the tolerance zone. This can substantially affect the size of the addition that must be added to the batch and/or can reduce the number of colorants required to achieve an in-tolerance match.

UTILITY skilled in the art of visual shading.

It should also be noted that this system can be used to adjust any physical property which can be mathematically expressed, e.g., gloss, hiding, etc. and predict adjustments to the batch accordingly.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The following example illustrate the various aspects of the invention in greater detail. However, it should be recognized that it is only illustrative. Variations from what is disclosed will undoubtedly occur to those skilled in the art, but will nevertheless be embraced by the inventive concept of the invention. All parts unless otherwise indicated are by weight.

EXAMPLE A batch of metallic gold paint was color standardized in accord with the following:

1. A batch of paint was prepared which would be the color standard to which subsequent batches would be shaded.

2.Paints were prepared for each of the pigments contained in the paint of (1), each paint containing only one pigment and a set amount of aluminum flake. These paints were prepared at two different pigment/aluminum ratios along with a sprayout of an aluminum paint and a single pigment paint.

3. The paints of (2) were sprayed on test panels under controlled environmental conditions and K, S valves calculated at 31 points across the visible spectrum (at 10 nanometer intervals from 400 to 700 nanometers) on a Bausch and Lomb 505 spectrophotometer modified to allow multi-angular determinations. This procedure. was performed at two angles -45 incident with 0 viewing angle and 25 incident with viewing angle measured from the normal to the panel.

4. Vector data were calculated for the standard paint from the K, S values using the Duncan and Kubelka- Munk equations.

Vector data for standard metallic goldpaint Colorant Conc. AL, Au, Abp AL Aa,, Ab

Hydrouslron Oxide 2.00 0.80 +0.56+l.17 0.36 +0.40 +0.65

Ferrite Yellow l.00 l.46 0.09i-2.l9 +l.5l -0.47 +2.58

Med. Coarse Aluminum 5.00 +2.95 l.432.59 +1.06 O.97 -l.53 White 0.25 l.22 0.050.34 +2.28 +0.63 +0.67 Back 0.75 2.28 0.86l.45 l.74-0.98 l.44 Orange 0.50 0.74 +l.72+0.ll 0.32 +l.00 +0.26

The above data are for the aforementioned dual angle positions- F (representing flat or 45, 0) and H (representing high or 25, 70). 7

The above vector data were punched onto a computer input card for shading reference.

5.,A subsequent batch of metallic gold paint was prepared. In order to color shade this according to the constants already derived, a test panel was sprayed with the non-standardized paint using the same spray technique which was used to spray the standard paint. Readings were made on this test panel at the same angles- 45 incident with 0 viewing angle and 25 incident with 70 viewing angle using a Colormaster colorimeter adapted to allow for multiangular measurements.

The color differences between the test panel and the standard were as follows:

AL,- +2.76 AL -l .03 Aa,-= 2.43 Aa,,=l.89 Ab,-=I.24 Ab,,=-I.32

6. The aforementioned color differences were fed into a programmed analog computer available from Electronics Associates along with the computer input card containing the vector data for the standard. The calculated color addition required for a 5,000-gram batch was:

The theoretical color differences, as predicted by the computer, afterthe above addition were:

1. An apparatus for instrumentally shading colors according to a standard color in the manufacture of paints containing light reflecting particles comprising A. means for determining color constants (vector data) by use of spectral curves at multi angles on a test panel coated with a standard paint;

B. means for determining differences at multi angles between the standard paint and a non-standard paint by use of tristimulus values; and,

C. means for correlating differences of (B) with the color constants of (A) and calculating proper amounts of specific pigments which should be added to the non-standard paint to obtain a color match.

2. The apparatus of claim 1 wherein A. the means for determining color constants (vector data) by use of spectral curves on a test panel coated with a standard paint is a spectrophotometer modified in order that multi-angular measurements can be made;

B. the means for determining color differences between the stand and a non-standard paint by use of tristimulus values is a colorimeter modified in order that multi-angular measurements can be made; and,

C. the means for correlating the differences of (B) with the color constants of (A) and calculating proper amounts of specific pigments which should be added to the non-standard paint to obtain a color match is a computer specially programmed to resolve the equations:

"AL NC ALF NC AL NCpaALpa NC AL -Aa NC AG NC AC NC Aap NC A m Abp NfpgAb NC Ab NCpaA bps i NC A Aa NC AQ NC AC i NC Aa HN IIN N mv mv where F and H represents two different angles.

3. A method of instrumentally color shading paints containing light reflecting metal flakes comprising A. deriving color constants (vector data) for a test panel coated with standard paint by multiangular spectrophotometric determinations;

B. determining differences between the test panel and a panel similarly coated with paint from a batch which is to be shaded by obtaining tristimulus values using a colorimeter at the same angles as the aforementioned spectrophotometric determinations; and C. correlating the aforementioned differences and color constants and calculating amounts of specific pigment which should be added to the non-standardized batch to produce a color match with the standard paint.

4. The method of claim 3 wherein the standard and non-standard paints contain metallics and the color constants (vector data) for the standard paint are determined by multi-angular spectrophotometric measurements on panels coated individually with each pigment contained in the standard paint and a panel coated with only metal flake.

5. The method of claim 4 wherein the multi-angular measurements are limited to two angles which differ from each other by from 60 to 80, said same angles being used for measurement by the spectrophotometer and colorimeter.

6. The method of claim 3 wherein a computer is used for correlating differences between the standard and non-standard paint and calculating amounts of pigment to be added to obtain a color match, said computer programmed to handle the equations:

AL Ncp ALp NCpgALpz 'i" NCpaALpg NC AL 40 Aap= NC Aa NCpgACm NcpaAapa NC A Abp= NCpzAbp NcpzAhpg NCp Ab 3 NC A FN "AL NC AL NCHZALHz NC AL HN HN Aa NC nAG NC AC NC 3Aa NC AG Ab =NC Ab +NCH2AbH2+NCH3AbH3+ i NCH Ab where F and H represent two different angles.

Claims (6)

1. An apparatus for instrumEntally shading colors according to a standard color in the manufacture of paints containing light reflecting particles comprising A. means for determining color constants (vector data) by use of spectral curves at multi angles on a test panel coated with a standard paint; B. means for determining differences at multi angles between the standard paint and a non-standard paint by use of tristimulus values; and, C. means for correlating differences of (B) with the color constants of (A) and calculating proper amounts of specific pigments which should be added to the non-standard paint to obtain a color match.
2. The apparatus of claim 1 wherein A. the means for determining color constants (vector data) by use of spectral curves on a test panel coated with a standard paint is a spectrophotometer modified in order that multi-angular measurements can be made; B. the means for determining color differences between the stand and a non-standard paint by use of tristimulus values is a colorimeter modified in order that multi-angular measurements can be made; and, C. the means for correlating the differences of (B) with the color constants of (A) and calculating proper amounts of specific pigments which should be added to the non-standard paint to obtain a color match is a computer specially programmed to resolve the equations: - Delta LF NcF1 Delta LF1 + NcF2 Delta LF2 + NcF3 Delta LF3 + . . . + NcFN Delta LFN - Delta aF NcF1 Delta aF1 + NcF2 Delta cF2 + NcF3 Delta aF3 + . . . + NcFN Delta aFN - Delta bF NcF2 Delta bF1 + NcF2 Delta bF2 + NcF3 Delta bF3 + . . . + NcFN Delta bFN - Delta LH NcH1 Delta LH1 + NcH2 Delta LH2 + NcH3 Delta LH3 + . . . + NcHN Delta LHN - Delta aH NcH1 Delta aH1 + NcH2 Delta cH2 + NcH3 Delta aH3 + . . . + NcHN Delta aHN - Delta bH NcH1 Delta bH1 + NcH2 Delta bH2 + NcH3 Delta bH3 + . . . + NcHN Delta bHN where F and H represents two different angles.
3. A method of instrumentally color shading paints containing light reflecting metal flakes comprising A. deriving color constants (vector data) for a test panel coated with standard paint by multiangular spectrophotometric determinations; B. determining differences between the test panel and a panel similarly coated with paint from a batch which is to be shaded by obtaining tristimulus values using a colorimeter at the same angles as the aforementioned spectrophotometric determinations; and C. correlating the aforementioned differences and color constants and calculating amounts of specific pigment which should be added to the non-standardized batch to produce a color match with the standard paint.
4. The method of claim 3 wherein the standard and non-standard paints contain metallics and the color constants (vector data) for the standard paint are determined by multi-angular spectrophotometric measurements on panels coated individually with each pigment contained in the standard paint and a panel coated with only metal flake.
5. The method of claim 4 wherein the multi-angular measurements are limited to two angles which differ from each other by from 60* to 80*, said same angles being used for measurement by the spectrophotometer and colorimeteR.
6. The method of claim 3 wherein a computer is used for correlating differences between the standard and non-standard paint and calculating amounts of pigment to be added to obtain a color match, said computer programmed to handle the equations: -Delta LF NcF1 Delta LF1 + NcF2 Delta LF2 + NcF3 Delta LF3 + . . . + NcFN Delta LFN - Delta aF NcF1 Delta aF1 + NcF2 Delta cF2 + NcF3 Delta aF3 + . . . + NcFN Delta aFN - Delta bF NcF2 Delta bF1 + NcF2 Delta hF2 + NcF3 Delta bF3 + . . . + NcFN Delta bFN -Delta LH NcH1 Delta LH1 + NcH2 Delta LH2 + NcH3 Delta LH3 + . . . + NcHN Delta LHN - Delta aH NcH1 Delta aH1 + NcH2 Delta cH2 + NcH3 Delta aH3 + . . . + NcHN Delta aHN - Delta bH NcH1 Delta bH1 + NcH2 Delta bH2 + NcH3 Delta bH3 + . . . + NcHN Delta bHN where F and H represent two different angles.
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US4479718A (en) * 1982-06-17 1984-10-30 E. I. Du Pont De Nemours And Company Three direction measurements for characterization of a surface containing metallic particles
US4546007A (en) * 1983-05-21 1985-10-08 Yoshiaki Abe Multi-layer coating method based on spectral reflectance of white or gray colors
US4552780A (en) * 1983-09-27 1985-11-12 Yoshiaki Abe Multi-layer coating method based on differential spectral reflectance
US4572672A (en) * 1982-02-19 1986-02-25 Imperial Chemical Industries Plc Surface coating characterization method and apparatus
US4597670A (en) * 1983-12-01 1986-07-01 Sumitomo Chemical Company, Limited Method of measuring color difference of dyestuffs
US4615902A (en) * 1985-09-03 1986-10-07 E. I. Du Pont De Nemours And Company Color panel standards sorting system
US4711580A (en) * 1985-01-28 1987-12-08 Hunter Associates Laboratory, Inc. Modeling properties of flake finishes using directional resolution and statistical flake orientation distribution function
EP0308741A2 (en) * 1987-09-22 1989-03-29 BASF Magnetics GmbH Procedure of controlling the dispersivity of magnetic pigments in a dispersion
US4841140A (en) * 1987-11-09 1989-06-20 Honeywell Inc. Real-time color comparator
US4917495A (en) * 1988-12-20 1990-04-17 E. I. Du Pont De Nemours And Company Portable colorimeter and method for characterization of a colored surface
US5023814A (en) * 1985-02-15 1991-06-11 Guillemin Jean Pierre H B Method and apparatus for countertyping a tint from a collection of base tints
US5231472A (en) * 1991-09-16 1993-07-27 Ppg Industries, Inc. Color matching and characterization of surface coatings
US5319437A (en) * 1991-07-26 1994-06-07 Kollmorgen Corporation Handheld portable spectrophotometer
WO1994025839A1 (en) * 1993-05-05 1994-11-10 E.I. Du Pont De Nemours And Company Rapid color shading process
US5387977A (en) * 1991-09-04 1995-02-07 X-Rite, Incorporated Multiangular color measuring apparatus
WO1998053285A1 (en) * 1997-05-17 1998-11-26 Herberts Gesellschaft mit beschränkter Haftung Method for calculating dye formulations of pigmented effect dyeing tones
US5907495A (en) * 1997-06-27 1999-05-25 General Motors Corporation Method of formulating paint through color space modeling
EP0932038A1 (en) * 1998-01-26 1999-07-28 Kansai Paint Co. Ltd. Method for classifying and arranging metallic paint colors
US6628393B1 (en) * 1998-07-28 2003-09-30 Basf Coatings Ag Method for determining the shade stability of lacquers
US20040131756A1 (en) * 2002-11-21 2004-07-08 Skierski Thomas J. Method of color matching wood stains
US20040223149A1 (en) * 2003-03-27 2004-11-11 Skierski Thomas J. Method of verifying color and strength properties of batches of wood stains
US20040252883A1 (en) * 2003-06-11 2004-12-16 Uwe Johansson Recipe calculation method for matt color shades
US20050083529A1 (en) * 2003-10-07 2005-04-21 Vogel Randall A. Effect-particle orientation and apparatus therefor
WO2006052561A2 (en) * 2004-11-05 2006-05-18 E.I. Dupont De Nemours And Company Computer-implemented color adjustment method and program using multi-dimensional vector analysis
US20070003691A1 (en) * 2005-05-05 2007-01-04 Rodrigues Allan B J Color clustering technique for matching refinish paints
US7167246B1 (en) 2002-07-12 2007-01-23 The Sherwin-Williams Company Method of color matching metallic paints
US7423755B2 (en) 2005-12-05 2008-09-09 E.I. Du Pont De Nemours And Company Liquid measurement cell having a transparent partition therein
US7477394B2 (en) 2005-12-05 2009-01-13 E.I Du Pont De Nemours & Company Method for measuring a color property of a liquid using a liquid measurement cell having a transparent partition therein
US7542143B2 (en) 2005-12-05 2009-06-02 E.I. Du Pont De Nemours And Company Liquid measurement cell having a pressurized air cavity therein
US7684045B2 (en) 2005-12-05 2010-03-23 E.I. Du Pont De Nemours And Company Probe apparatus for measuring a color property of a liquid
CN103926203A (en) * 2014-04-29 2014-07-16 中国科学院遥感与数字地球研究所 Spectral angle mapping method aiming at ground object spectrum uncertainty
WO2014159810A1 (en) * 2013-03-14 2014-10-02 Ppg Industries Ohio, Inc. Systems and methods for multi-flux color matching
US20150070694A1 (en) * 2013-09-11 2015-03-12 GM Global Technology Operations LLC Method and system for characterizing color variation of a surface
US9601081B2 (en) 2011-10-28 2017-03-21 Axalta Coating Systems Ip Co., Llc Process for displaying and designing colors

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US4572672A (en) * 1982-02-19 1986-02-25 Imperial Chemical Industries Plc Surface coating characterization method and apparatus
US4479718A (en) * 1982-06-17 1984-10-30 E. I. Du Pont De Nemours And Company Three direction measurements for characterization of a surface containing metallic particles
US4546007A (en) * 1983-05-21 1985-10-08 Yoshiaki Abe Multi-layer coating method based on spectral reflectance of white or gray colors
US4552780A (en) * 1983-09-27 1985-11-12 Yoshiaki Abe Multi-layer coating method based on differential spectral reflectance
US4597670A (en) * 1983-12-01 1986-07-01 Sumitomo Chemical Company, Limited Method of measuring color difference of dyestuffs
US4711580A (en) * 1985-01-28 1987-12-08 Hunter Associates Laboratory, Inc. Modeling properties of flake finishes using directional resolution and statistical flake orientation distribution function
US5023814A (en) * 1985-02-15 1991-06-11 Guillemin Jean Pierre H B Method and apparatus for countertyping a tint from a collection of base tints
US4615902A (en) * 1985-09-03 1986-10-07 E. I. Du Pont De Nemours And Company Color panel standards sorting system
EP0308741A2 (en) * 1987-09-22 1989-03-29 BASF Magnetics GmbH Procedure of controlling the dispersivity of magnetic pigments in a dispersion
EP0308741A3 (en) * 1987-09-22 1990-09-19 Agfa-Gevaert Ag Apparatus for determining the dispersion rate of magnetic pigments in a dispersion
US4841140A (en) * 1987-11-09 1989-06-20 Honeywell Inc. Real-time color comparator
US4917495A (en) * 1988-12-20 1990-04-17 E. I. Du Pont De Nemours And Company Portable colorimeter and method for characterization of a colored surface
US5319437A (en) * 1991-07-26 1994-06-07 Kollmorgen Corporation Handheld portable spectrophotometer
US5483339A (en) * 1991-07-26 1996-01-09 Killmorgen Corporation Spectrophotometer and radiometric measurement apparatus
US5387977A (en) * 1991-09-04 1995-02-07 X-Rite, Incorporated Multiangular color measuring apparatus
US5231472A (en) * 1991-09-16 1993-07-27 Ppg Industries, Inc. Color matching and characterization of surface coatings
WO1994025839A1 (en) * 1993-05-05 1994-11-10 E.I. Du Pont De Nemours And Company Rapid color shading process
US5371599A (en) * 1993-05-05 1994-12-06 E. I. Du Pont De Nemours And Company Rapid color shading process
WO1998053285A1 (en) * 1997-05-17 1998-11-26 Herberts Gesellschaft mit beschränkter Haftung Method for calculating dye formulations of pigmented effect dyeing tones
US6064487A (en) * 1997-05-17 2000-05-16 Herberts Gmbh Method for calculating dye formulations of pigmented effect dyeing tones
US5907495A (en) * 1997-06-27 1999-05-25 General Motors Corporation Method of formulating paint through color space modeling
US6992277B2 (en) 1998-01-26 2006-01-31 Kansai Paint Co., Ltd. Method for classifying and arranging metallic paint colors
US20040179023A1 (en) * 1998-01-26 2004-09-16 Yutaka Masuda Method for classifying and arranging metallic paint colors
US6747662B2 (en) 1998-01-26 2004-06-08 Kansai Paint Co., Ltd. Method for classifying and arranging metallic paint colors
EP0932038A1 (en) * 1998-01-26 1999-07-28 Kansai Paint Co. Ltd. Method for classifying and arranging metallic paint colors
US6628393B1 (en) * 1998-07-28 2003-09-30 Basf Coatings Ag Method for determining the shade stability of lacquers
US7167246B1 (en) 2002-07-12 2007-01-23 The Sherwin-Williams Company Method of color matching metallic paints
US7116420B2 (en) 2002-11-21 2006-10-03 The Sherwin-Williams Company Method of color matching wood stains
US20040131756A1 (en) * 2002-11-21 2004-07-08 Skierski Thomas J. Method of color matching wood stains
US7042566B2 (en) 2003-03-27 2006-05-09 The Sherwin-Williams Company Method of verifying color and strength properties of batches of wood stains
US20040223149A1 (en) * 2003-03-27 2004-11-11 Skierski Thomas J. Method of verifying color and strength properties of batches of wood stains
US20040252883A1 (en) * 2003-06-11 2004-12-16 Uwe Johansson Recipe calculation method for matt color shades
US7158672B2 (en) 2003-06-11 2007-01-02 E. I. Du Pont De Nemours And Company Recipe calculation method for matt color shades
US7375335B2 (en) 2003-10-07 2008-05-20 E. I. Du Pont De Nemours And Company Effect-particle orientation and apparatus therefor
US20050083529A1 (en) * 2003-10-07 2005-04-21 Vogel Randall A. Effect-particle orientation and apparatus therefor
WO2006052561A3 (en) * 2004-11-05 2006-07-06 Du Pont Computer-implemented color adjustment method and program using multi-dimensional vector analysis
WO2006052561A2 (en) * 2004-11-05 2006-05-18 E.I. Dupont De Nemours And Company Computer-implemented color adjustment method and program using multi-dimensional vector analysis
US20070003691A1 (en) * 2005-05-05 2007-01-04 Rodrigues Allan B J Color clustering technique for matching refinish paints
US7684045B2 (en) 2005-12-05 2010-03-23 E.I. Du Pont De Nemours And Company Probe apparatus for measuring a color property of a liquid
US7423755B2 (en) 2005-12-05 2008-09-09 E.I. Du Pont De Nemours And Company Liquid measurement cell having a transparent partition therein
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US20150070694A1 (en) * 2013-09-11 2015-03-12 GM Global Technology Operations LLC Method and system for characterizing color variation of a surface
US9200999B2 (en) * 2013-09-11 2015-12-01 GM Global Technology Operations LLC Method and system for characterizing color variation of a surface
CN103926203B (en) * 2014-04-29 2016-04-20 中国科学院遥感与数字地球研究所 A spectroscopic method of mapping the uncertainty of the angle feature for spectra
CN103926203A (en) * 2014-04-29 2014-07-16 中国科学院遥感与数字地球研究所 Spectral angle mapping method aiming at ground object spectrum uncertainty

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CA989976A (en) 1976-05-25 grant
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BE765205A (en) 1971-08-30 grant
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